Method for producing triazolinethione derivatives

ABSTRACT

According to a novel process, triazolinethione derivatives of the formula                    
     in which R 1  and R 2  are each as defined in the description, 
     can be prepared by 
     a) reacting hydrazine derivatives of the formula                    
      with formaldehyde and thiocyanate of the formula 
     
       
         X—SCN  (III), 
       
     
      in which 
     X represents sodium, potassium or ammonium, 
      in the presence of a diluent and if appropriate in the presence of an acid, and 
     b) reacting the resulting triazolidinethiones of the formula                    
      either 
     α) with oxidizing agents, if appropriate in the presence of a catalyst and in the presence of a diluent, or 
     β) with formic acid. 
     The triazolidinethiones of the formula (IV) are novel.

This application is a divisional of Ser. No. 09/509,763, filed Mar. 28,2000 now U.S. Pat. No. 6,201,128 B1, which is a 371 of PCT/EP98/06112,filed Sep. 25, 1998.

The present invention relates to a novel process for preparingtriazolinethione derivatives which are known as active compounds havingmicrobicidal, in particular fungicidal, properties.

It is already known that triazolinethione derivatives can be prepared byeither reacting the corresponding triazole derivatives successively withstrong bases and sulphur and then hydrolysing them, or reacting themdirectly with sulphur at high temperatures, followed by treatment withwater (cf. WO-A 96-16 048). However, this process has the disadvantagethat the desired products are obtained in only relatively low yields, orthat reaction conditions are required which are difficult to maintain onan industrial scale.

Furthermore, it has already been described that certain1,2,4-triazoline-5-thiones substituted in the 3 position can be preparedby reacting N-chlorothioformyl-N-(1-chloroalk-1-ene)-amines withcarbonylhydrazine derivatives (cf. DE-A 197 01 032, DE-A 196 01 189 andEP-A 0 784 053). However, the synthesis of corresponding substanceswhich do not have a substituent in the 3 position is not mentioned.

Furthermore, Bull. Chem. Soc. Japan 46, 2215 (1973) discloses thattriazolinethiones substituted in the 3 position can be synthesized byreacting phenylhydrazine with sodium thiocyanate and ketones oraldehydes in the presence of hydrochloric acid and treating theresulting triazolidinethiones substituted in the 3 position withoxidizing agents. This process has the disadvantages that very longreaction times are required and that no triazolinethiones which areunsubstituted in the 3 position can be obtained in this manner.

Finally, it is also known that2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-3-(1,2,4-triazol-1-yl)-propan-2-olis obtained when[1-(2-chloro-phenyl)-2-(1-chloro-cycloprop-1-yl)-2-hydroxy]-propyl-hydrazineis reacted with formamidine acetate (cf. DE-A 40 30 039). However,thiono derivatives of triazoles are not obtainable by this method.

It has now been found that triazolinethione derivatives of the formula

in which

R¹ and R² are identical or different and each represents optionallysubstituted alkyl, optionally substituted alkenyl, optionallysubstituted cycloalkyl, optionally substituted aralkyl, optionallysubstituted aralkenyl, optionally substituted aroxyalkyl, optionallysubstituted aryl or optionally substituted heteroaryl,

can be prepared by

a) reacting, in a first step, hydrazine derivatives of the formula

 in which

R¹ and R² are each as defined above

 with formaldehyde and thiocyanate of the formula

 X—SCN  (III),

 in which

X represents sodium, potassium or ammonium,

 in the presence of a diluent and if appropriate in the presence of anacid, and

b) reacting the resulting triazolidinethiones of the formula

 in which

R¹ and R² are each as defined above

 in a second step either

α) with oxidizing agents, if appropriate in the presence of catalyst andin the presence of a diluent, or

β) with formic acid of the formula

HCOOH  (V).

It is extremely surprising that triazolinethione derivatives of theformula (I) can be prepared by the process according to the invention insubstantially higher yields or under considerably simpler conditionsthan by the prior-art methods.

The process according to the invention has a number of advantages. Thus,as already mentioned, it makes it possible to synthesizetriazolinethiones of the formula (I) in high yield. It is alsofavourable that the required starting materials and reaction componentscan be prepared in a simple manner and are available even in relativelylarge amounts. A further advantage consists in the fact that theindividual reaction steps can be carried out and the reaction productscan be isolated without any problems.

Using[1-(2-chloro-phenyl)-2-(1-chloro-cycloprop-1-yl)-2-hydroxy]-propyl-1-hydrazineas starting material and reacting this in the first step withparaformaldehyde and ammonium thiocyanate and allowing the resultingproduct to react in the second step with oxygen in the presence ofpotassium hydroxide and sulphur, the course of the process according tothe invention can be illustrated by the scheme below.

The formula (II) provides a general definition of the hydrazinederivatives required as starting materials for carrying out the processaccording to the invention. Preference is given to using compounds ofthe formula (II) in which

R¹ represents straight-chain or branched alkyl having 1 to 6 carbonatoms, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting ofhalogen, alkoxy having 1 to 4 carbon atoms, alkoximino having 1 to 4carbon atoms in the alkoxy moiety and cycloalkyl having 3 to 7 carbonatoms, or

 represents straight-chain or branched alkenyl having 2 to 6 carbonatoms, where each of these radicals may be mono- to trisubstituted byidentical or different substituents from the group consisting ofhalogen, alkoxy having 1 to 4 carbon atoms and cycloalkyl having 3 to 7carbon atoms, or

 represents cycloalkyl having 3 to 7 carbon atoms, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, cyano and alkylhaving 1 to 4 carbon atoms, or

 represents aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1to 4 carbon atoms in the straight-chain or branched alkyl moiety, wherethe aryl moiety may in each case be mono- to trisubstituted by identicalor different substituents from the group consisting of halogen, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthiohaving 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or

 represents aralkenyl having 6 to 10 carbon atoms in the aryl moiety and2 to 4 carbon atoms in the alkenyl moiety, where the aryl moiety may ineach case be mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, alkyl having 1 to 4carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 or 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or

 represents aroxyalkyl having 6 to 10 carbon atoms in the aryl moietyand 1 to 4 carbon atoms in the straight-chain or branched oxyalkylmoiety, where the aryl moiety may in each case be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 or 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand cyano, or

 represents aryl having 6 to 10 carbon atoms, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, alkyl having 1 to 4carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 or 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cyloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or

 represents an optionally benzo-fused five- or six-memberedheteroaromatic radical having 1 to 3 heteroatoms, such as nitrogen,sulphur and/or oxygen, where each of these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, alkyl having 1 to 4 carbon atoms, hydroxyalkylhaving 1 to 4 carbon atoms, hydroxyalkinyl having 3 to 8 carbon atoms,alkoxy having 1 or 2 carbon atoms, alkylthio having 1 or 2 carbon atoms, halogenoalkyl, halogenoalkoxy and halogenoalkylthio having in eachcase 1 or 2 carbon atoms and 1 to 5 identical or different halogenatoms, such as fluorine or chlorine atoms, formyl, dialkoxymethyl having1 or 2 carbon atoms in each alkoxy group, acyl having 2 to 4 carbonatoms, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to3 carbon atoms in the alkyl moiety, nitro and cyano, and

R² represents straight-chain or branched alkyl having 1 to 6 carbonatoms, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting ofhalogen, alkoxy having 1 to 4 carbon atoms, alkoximino having 1 to 4carbon atoms in the alkoxy moiety and cycloalkyl having 3 to 7 carbonatoms, or

 represent s straight-chain or branched alkyl having 2 to 6 carbonatoms, where each of these radicals may be mono- to trisubstituted byidentical or different substituents from the group consisting ofhalogen, alkoxy having 1 to 4 carbon a toms and cycloalkyl having 3 to 7carbon atoms, or

 represents cycloalkyl having 3 to 7 carbon atoms, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, cyano and alkylhaving 1 to 4 carbon atoms, or

 represents aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1to 4 carbon atoms in the straight-chain or branched alkyl moiety, wherethe aryl moiety may in each case be mono- to trisubstituted by identicalor different substituents from the group consisting of halogen, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthiohaving 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or

 represents aralkenyl having 6 to 10 carbon atoms in the aryl moiety and2 to 4 carbon atoms in the alkenyl moiety, where the aryl moiety mayinitially be mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, alkyl having 1 to 4carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 or 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or

 represents aroxyalkyl having 6 to 10 carbon atoms in the aryl moietyand 1 to 4 carbon atoms in the straight-chain or branched oxyalkylmoiety, where the aryl moiety may in each case be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 or 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand cyano, or

 represents aryl having 6 to 10 carbon atoms, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, alkyl having 1 to 4carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 or 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or

 represents an optionally benzo-fused five- or six-memberedheteroaromatic radical having 1 to 3 heteroatoms, such as nitrogen,sulphur and/or oxygen, where each of these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, alkyl having 1 to 4 carbon atoms, hydroxyalkylhaving 1 to 4 carbon atoms, hydroxyalkinyl having 3 to 8 carbon atoms,alkoxy having 1 or 2 carbon atoms, alkylthio having 1 or 2 carbon atoms,halogenoalkyl, halogenoalkoxy and halogenoalkylthio having in each case1 or 2 carbon atoms and 1 to 5 identical or different halogen atoms,such as fluorine or chlorine atoms, formyl, dialkoxymethyl having 1 or 2carbon atoms in each alkoxy group, acyl having 2 to 4 carbon atoms,alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to3 carbon atoms in the alkyl moiety, nitro and cyano.

Particular preference is given to using hydrazine derivatives of theformula (II) in which

R¹ represents straight-chain or branched alkyl having 1 to 4 carbonatoms, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,alkoximino having 1 or 2 carbon atoms in the alkoxy moiety, cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl, or

 represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, where each of these radicals may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, or

 represents cycloalkyl having 3 to 6 carbon atoms, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,cyano, methyl, ethyl, propyl, isopropyl and tert-butyl, or

 represents phenylalkyl having 1 to 4 carbon atoms in the straight-chainor branched alkyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or

 represents phenylalkenyl having 2 to 4 carbon atoms in the alkenylmoiety, where the phenyl moiety may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or

 represents phenoxyalkyl having 1 to 4 carbon atoms in thestraight-chain or branched oxyalkyl moiety, where the phenyl moiety maybe mono- to trisubstituted by identical or different substituents fromthe group consisting of fluorine, chlorine, bromine, methyl, ethyl,tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,or

 represents phenyl which may be mono- to trisubstituted by identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or

 represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl,thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl,quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl,benzofuranyl, benzothiazolyl or benzimidazolyl, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,chlorodifluoromethylthio, hydroxymethyl, hydroxyethyl, hydroxyalkinylhaving 4 to 6 carbon atoms, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro, cyano, formyl,dimethoxymethyl, acetyl and propionyl, and

R² represents straight-chain or branched alkyl having 1 to 4 carbonatoms, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,alkoximino having 1 or 2 carbon atoms in the alkoxy moiety, cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl, or

 represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, where each of these radicals may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, or

 represents cycloalkyl having 3 to 6 carbon atoms, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,cyano, methyl, ethyl, propyl, isopropyl and tert-butyl, or

 represents phenylalkyl having 1 to 4 carbon atoms in the straight-chainor branched alkyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluorometboxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or

 represents phenylalkenyl having 2 to 4 carbon atoms in the alkenylmoiety, where the phenyl moiety may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluorometboxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or

 represents phenoxyalkyl having 1 to 4 carbon atoms in thestraight-chain or branched oxyalkyl moiety, where the phenyl moiety maybe mono- to trisubstituted by identical or different substituents fromthe group consisting of fluorine, chlorine, bromine, methyl, ethyl,tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,or

 represents phenyl which may be mono- to trisubstitued by identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or

 represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl,thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl,quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl,benzofuranyl, benzothiazolyl or benzimidazolyl, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,chlorodifluoromethylthio, hydroxymethyl, hydroxyethyl, hydroxyalkinylhaving 4 to 6 carbon atoms, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro, cyano, formyl,dimethoxymethyl, acetyl and propionyl.

Very particular preference is given to using hydrazine derivatives ofthe formula (II) in which

R¹ represents n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl ortert-butyl, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,methoximino, ethoximino, cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl, or

 represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, where each of these radicals may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, or

 represents 1-methyl-cyclohexyl, cyclohexyl, 1-chloro-cyclopropyl,1-fluoro-cyclopropyl, 1-methyl-cyclopropyl, 1-cyano-cyclopropyl,cyclopropyl, 1-methyl-cyclopentyl or 1-ethyl-cyclopentyl, or

 represents phenylalkyl having 1 or 2 carbon atoms in the straight-chainor branched alkyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or

 represents phenylalkenyl having 2 to 4 carbon atoms in the alkenylmoiety, where the phenyl moiety may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluormethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or

 represents phenoxyalkyl having 1 to 4 carbon atoms in thestraight-chain or branched oxyalkyl moiety, where the phenyl moiety maybe mono- to trisubstituted by identical or different substituents fromthe group consisting of fluorine, chlorine, bromine, methyl, ethyl,tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluormethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,or

 represents phenyl which may be mono- to trisubstituted by identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or

 represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl,thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl,quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl,benzofuranyl, benzothiazolyl or benzimidazolyl, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,chlorodifluoromethylthio, hydroxymethyl, hydroxyethyl, hydroxyalkinylhaving 4 to 6 carbon atoms, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro, cyano, formyl,dimethoxymethyl, acetyl and propionyl, and

R² represents n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl ortert-butyl, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,methoximino, ethoximino, cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl, or

 represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, where each of these radicals may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, or

 represents 1-methyl-cyclohexyl, cyclohexyl, 1-chloro-cyclopropyl,1-fluoro-cyclopropyl, 1-methyl-cyclopropyl, 1-cyano-cyclopropyl,cyclopropyl, 1-methyl-cyclopentyl or 1-ethyl-cyclopentyl, or

 represents phenylalkyl having 1 or 2 carbon atoms in the straight-chainor branched alkyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluormethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or

 represents phenylalkenyl having 2 to 4 carbon atoms in the alkenylmoiety, where the phenyl moiety may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or

 represents phenoxyalkyl having 1 to 4 carbon atoms in thestraight-chain or branched oxyalkyl moiety, where the phenyl moiety maybe mono- to trisubstituted by identical or different substituents fromthe group consisting of fluorine, chlorine, bromine methyl, ethyl,tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,or

 represents phenyl which may be mono- to trisubstituted by identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio,trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or

 represents pyrazolyl, imidazolyl, 1,2,4-triazolyl, pyrrolyl, furanyl,thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl,quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl,benzofuranyl, benzothiazolyl or benzimidazolyl, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy, chlorodifluoromethylthio, hydroxymethyl, hydroxyethyl, hydroxyalkinyl having 4to 6 carbon atoms, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl,1-methoximinoethyl, nitro, cyano, formyl, dimethoxymethyl, acetyl andpropionyl.

The hydrazine derivatives of the formula (II) are known or can beprepared by processes known in principle (cf. DE-A-40 30 039).

Thus, hydrazine derivatives of the formula (II) are obtained by reacting1-chloro-2-hydroxyethane derivatives of the formula

in which

R¹ and R² are each as defined above,

in the presence of an acid binder, such as potassium tert-butoxide,sodium methoxide or potassium carbonate, and in the presence of adiluent, such as dimethylformamide, methanol, n-butanol, tetrahydrofuranor methyl tert-butyl ether, at temperatures between 20° C. and 60° C.,and reacting the resulting oxirane derivatives of the formula

in which

R¹ and R² are each as defined above

with hydrazine hydrate, if appropriate in the presence of a diluent,such as methanol, n-butanol, tetrahydrofuran, methyl tert-butyl ether,dioxane or nitrites, such as acetonitrile, at temperatures between 30°C. and 120° C.

Particular preference is given to reacting the 1-chloro-2-hydroxy-ethanederivatives of the formula (VI) with excess hydrazine hydrate, actinghere both as reactant and as base and diluent.

The 1-chloro-2-hydroxy-ethane derivatives of the formula (VI) are knownor can be prepared by processes known in principle (cf. DE-A 40 30 039and EP-A 0 297 345).

The formaldehyde required as reaction component for carrying out thefirst step of the process according to the invention can be employed asparaformaldehyde, as gaseous formaldehyde or else as formalin solution(=aqueous formaldehyde solution).

Furthermore, thiocyanates of the formula (III) are employed as reactioncomponents when carrying out the first step of the process according tothe invention. The thiocyanates of the formula (III) are known.

Suitable diluents for carrying out the first step of the processaccording to the invention are all inert organic solvents which arecustomary for such reactions. Preference is given to using alcohols,such as n-butanol and tert-butanol, furthermore ethers such as dioxaneand methyl tert-butyl ether, moreover nitriles, such as acetonitrile,and hydrocarbons, such as toluene or chlorobenzene, in each case ifappropriate as a mixture with water.

Suitable acids for carrying out the first step of the process accordingto the invention are all customary inorganic and organic acids.Preference is given to using hydrochloric acid, sulphuric acid,p-toluenesulphonic acid and also sodium hydrogen sulphate in thepresence of water.

Both the first and the second step of the process according to theinvention are generally carried out under atmospheric pressure. However,it is also possible to operate under elevated pressure or, if no gaseouscomponents participate in the reaction, under reduced pressure.

When carrying out the first step of the process according to theinvention, generally from 1 to 2 mol of formaldehyde and from 1 to 2 molof thiocyanate of the formula (III) and, if appropriate, an equivalentamount of acid or sodium hydrogen sulphate and water, where the watermay also be present in excess, are employed per mole of hydrazinederivative of the formula (II). Work-up is carried out by customarymethods. If the reaction is carried out in the absence of water, thereaction mixture is, if appropriate after prior dilution with an organicsolvent which is sparingly water-miscible, generally washed withaqueous-alkaline solution, and the organic phase is dried andconcentrated. If the reaction is carried out in the presence of waterand in the presence of sodium hydrogen sulphate, the reaction mixture isgenerally diluted with an organic solvent which is sparinglywater-miscible, filtered and concentrated under reduced pressure. Anyimpurities which may then still be present can be removed by customarymethods, such as recrystallization or chromatography.

The formula (IV) provides a general definition of thetriazolidinethiones required as starting materials for carrying out thesecond step of the process according to the invention. In this formula,R¹ and R² preferably have those meanings which have already beenmentioned in connection with the description of the hydrazinederivatives of the formula (II) as being preferred for these radicals.

The triazolidinethiones of the formula (IV) have hitherto not beendisclosed. They can be prepared by the reaction of the first step of theprocess according to the invention.

Preferred oxidizing agents for carrying out the second step of theprocess according to the invention according to variant (α) are oxygen,sulphur and potassium peroxide. If the oxidizing agent used is oxygen,this is preferably added in the form of air.

Preferred catalyst for carrying out the second step of the processaccording to the invention according to variant (α) is a mixture ofpotassium hydroxide and sulphur powder. This catalyst is preferablyemployed when the oxidizing agent used is oxygen.

Suitable diluents for carrying out the second step of the processaccording to the invention according to variant (α) are all inertorganic solvents which are customary for such reactions. Preference isgiven to using aliphatic, cycloaliphatic and aromatic hydrocarbons, suchas pentane, hexane, cyclohexane, benzene, toluene and xylene,furthermore ethers, such as methyl tert-butyl ether, and also esters,such as n-butyl acetate.

When carrying out the second step of the process according to theinvention according to variant (α), the reaction temperatures can bevaried within a relatively wide range. In general, the reaction iscarried out at temperatures between 0° C. and 120° C. If the oxidizingagent used is oxygen, the reaction is preferably carried out attemperatures between 20° C. and 80° C. If the oxidizing agent used issulphur, the reaction is preferably carried out at temperatures between50° C. and 110° C. If the oxidizing agent used is potassium peroxide,the reaction is preferably carried out at temperatures between 20° C.and 80° C.

When carrying out the second step of the process according to theinvention according to variant (α), in general an excess of oxidizingagent is used per mole of triazolidinethione of the formula (IV). If theoxidizing agent used is sulphur or potassium peroxide, preference isgiven to using from 1.5 to 2 mol of oxidizing agent per mole oftriazolidinethione of the formula (IV). If the oxidizing agent used isoxygen in the form of air, preference is given to passing a stream ofair through the reaction mixture until the reaction has ended. Work-upis in each case carried out by customary methods. In general, thereaction mixture is, if appropriate after prior dilution with an organicsolvent which is sparingly water-miscible, extracted with aqueous saltsolution, and the organic phase is dried and concentrated. Anyimpurities which may then still be present can be removed by customarymethods, such as recrystallization or chromatography. However, it isalso possible to isolate the product as the potassium salt and then toliberate the product by addition of acid.

When carrying out the second step of the process according to theinvention according to variant (β), the reaction temperatures canlikewise be varied within a certain range. In general, the reaction iscarried out at temperatures between 50° C. and 100° C.

When carrying out the second step of the process according to theinvention according to variant (β), formic acid acts both as reactioncomponent and as diluent. Thus, in general a high excess of formic acidis employed per mole of triazolidinethione of the formula (IV). Oncemore, work-up is carried out by customary methods. In general, thereaction mixture is concentrated under reduced pressure and the desiredproduct is isolated from the residue that remains by recrystallizationand/or by chromatographic means.

In a particular variant, the process according to the invention can becarried out such that 1-chloro-2-hydroxy-ethane derivatives of theformula (VI) are reacted with hydrazine hydrate and the resultinghydrazine derivatives of the formula (II) are then reacted furtherwithout prior isolation. Thus, triazolinethiones of the formula (I) canalso be prepared by

reacting 1-chloro-2-hydroxy-ethane derivatives of the formula

 in which

R¹ and R² are each as defined above

 with hydrazine hydrate, if appropriate in the presence of a diluent,

reacting the resulting hydrazine derivatives of the formula

 in which

R¹ and R² are each as defined above

 without prior isolation with formaldehyde and thiocyanate of theformula

X—SCN  (III),

 in which

X represents sodium, potassium or ammonium,

 in the presence of a diluent and if appropriate in the presence of anacid, and reacting the resulting triazolidinethiones of the formula

 in which

R¹ and R² are each as defined above

 either

α) with oxidizing agents, if appropriate in the presence of a catalystand in the presence of a diluent, or

β) with formic acid of the formula

HCOOH  (V).

Suitable diluents for carrying out the first step of this variant of theprocess according to the invention are all customary inert organicsolvents. Preference is given to using alcohols, such as n-butanol, andethers, such as dioxane or methyl tert-butyl ether, and also nitrites,such as acetonitrile. However, it is also possible to carry out thereaction without additional solvent. In this case, hydrazine hydrate isemployed in excess, so that it acts both as reaction component and asdiluent.

When carrying out the first step of this variant of the processaccording to the invention, the reaction temperatures can be variedwithin a certain range. In general, the reaction is carried out attemperatures between 60° C. and 120° C., preferably between 70° C. and100° C.

The first step of this variant of the process according to the inventionis preferably carried out such that between 3 and 20 mol, particularlypreferably between 4 and 15 mol, of hydrazine hydrate are employed permole of 1-chloro-2-hydroxy-ethane derivative of the formula (VI), andthe mixture is then diluted with an organic solvent which is sparinglywater-miscible, such as methyl tert-butyl ether, the aqueous phase isseparated off, and the organic phase is washed and dried and then usedfor the subsequent reactions without any further work-up.

The other steps of this variant of the process according to theinvention are carried out in the manner described above.

The triazolinethione derivatives preparable according to the inventioncan be present in the “thiono” form of the formula

or in the tautomeric “mercapto” form of the formula

For the sake of simplicity, only the “thiono” form is shown in eachcase.

The triazolinethione derivatives preparable according to the inventionare known as active compounds having microbicidal, in particularfungicidal, properties (cf. WO A 96-16048).

The practice of the process according to the invention is illustrated bythe examples below.

PREPARATION EXAMPLES Example 1

a) Preparation of the compound of the formula

With stirring, a mixture of 5.48 g (20 mmol) of[2-(1-chloro-cycloprop-1-yl)-3(2-chlorophenyl)-2-hydroxy]-propyl-1-hydrazine, 40 ml of methyltert-butyl ether, 0.9 g (30 mmol) of paraformaldehyde and 1.84 g (24mmol) of ammonium thiocyanate is heated at 60° C. for 3 hours. Aftercooling to room temperature, the reaction mixture is diluted with methyltert-butyl ether and washed with saturated aqueous sodium carbonatesolution. The organic phase is dried over sodium sulphate, filtered andconcentrated under reduced pressure. This gives 6.1 g of a productwhich, according to HPLC analysis, comprises 86.9% of2-(1-chloro-cycloprop1-yl)-1-(2-chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiono-1-yl)-propane. After addition of a littledichloromethane,2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiono-1-yl)-propaneprecipitates out in the form of a crystalline solid.

Melting point: 152-154° C.

¹H NMR spectrum (CDCl₃, TMS, 250 MHz): δ=0.8-1.3 (m,3H); 3.1 (d, J=14Hz, 1H); 3.65 (d, J=14 Hz, 1H); 4.2 (s,2H); 4.45-4.65 (m,3H); 5.1 (t,NH); 7.15-7.6 (m,4H) ppm

b) Preparation of the compound of the formula

With stirring, a stream of air is passed for 3.5 hours over a mixture of1.72 g (5 mmol) of2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiono-1-yl)-propane,10 ml of absolute toluene, 0.34 g (6 mmol) of potassium hydroxide powderand 10 mg of sulphur powder which had been heated to 70° C. The progressof the reaction is monitored by HPLC analysis. After cooling to roomtemperature, the reaction mixture is diluted with methyl tert-butylether and washed repeatedly with saturated aqueous ammonium chloridesolution. The organic phase is dried over sodium sulphate, filtered andconcentrated under reduced pressure. This gives 2.2 g of a productwhich, according to HPLC analysis, comprises 71% of2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-3-(4,5-dihydro-1,2,4-triazole-5-thiono-1-yl)-propan-2-ol.After recrystallization from toluene, the substance has a melting pointof from 136 to 138° C.

Example 2

a) Preparation of the compound of the formula

With stirring, a mixture of 2.78 g (10 mmol) of3-chloro-2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-propan-2-ol and4.9 ml (100 mmol) of hydrazine hydrate is heated at 80° C. for 3 hours.The reaction mixture is then cooled to 20° C., 15 ml of methyltert-butyl ether are added and the aqueous phase is separated off. Theorganic phase is washed once with 5 ml of water and then dried over 1 gof sodium sulphate. The reaction mixture is then filtered, admixed with0.3 g (10 mmol) of paraformaldehyde and 0.76 g (20 mmol) of ammoniumthiocyanate and heated with stirring at from 55 to 60° C. for 3 hours.The mixture is allowed to cool to room temperature, admixed with methyltert-butyl ether and washed three times with saturated aqueous ammoniumchloride solution. The organic phase is dried over sodium sulphate,filtered and concentrated under reduced pressure. This gives 2.4 g of aproduct which, according to HPLC analysis, comprises 68.3% of2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiono-1-yl)-propane.After addition of a little dichloromethane,2-(1-chloro-cycloprop-1-yl-1-(2-chloro-phenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiono-1-yl)-propaneprecipitates out in the form of a crystalline solid.

Melting point: 152-154° C.

b) Preparation of the compound of the formula

With stirring, a mixture of 1.71 g (5 mmol) of2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiono-1-yl)-propane,12.5 ml of n-butyl acetate and 0.25 g (7.5 mmol) of sulphur powder isheated at 100° C. for 9 hours, during which the progress of the reactionis monitored by HPLC analysis. The reaction mixture is then cooled toroom temperature, diluted with methyl tert-butyl ether and washedrepeatedly with saturated aqueous ammonium chloride solution. Theorganic phase is dried over sodium sulphate, filtered and concentratedunder reduced pressure. This gives 2.5 g of a product which, accordingto HPLC analysis, comprises 72.2% of2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-3-(4,5-dihydro-1,2,4-triazole-5-thiono-1-yl)-propan-2-ol.After recrystallization from toluene, the substance has a melting pointof from 137 to 138° C.

Example 3

Under an atmosphere of nitrogen and with stirring, a mixture of 27.8 g(0.1 mol) of3-chloro-2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-propan-2-ol and48.5 ml (1 mol) of hydrazine hydrate is heated at 100° C. for 5 hours.After cooling of the two-phase system to room temperature, the hydrazinephase is decanted off and the residue is washed once with 20 ml ofwater. This gives 25.9 g of a product which, according togaschromatographic analysis, comprises 86.8% of2-(1-chloro-cycloprop-1-yl)-3-(2-chloro-phenyl)-2-hydroxy-propyl-1-hydrazine.Accordingly, the calculated yield is 94.5% of theory. Recrystallizationof the crude product from acetonitrile gives2-(1-chloro-cycloprop-1-yl)-3-(2-chloro-phenyl)-2-hydroxy-propyl-1-hydrazinein the form of a solid of melting point 86° C. to 88° C.

¹H NMR spectrum (400 MHz, CDCl₃, TMS): δ=0.8-1.05 (m,3H); 1.25 (m,1H);2.7 (d,1H); 2.95 (d,1H); 3.45 (d,1H); 3.6 (d,1 H); 2.8-3.5 (3H,NH); 4.6(1H,OH); 7.1-7.5 (m,4H) ppm

Example 4

At 0° C. and under an atmosphere of nitrogen, a mixture of 2.74 g (10mmol) of [2-(1-chloro-cycloprop-1-yl)-3-(2-chlorophenyl)-2-hydroxy]-propyl-1-hydrazine (which had been recrystallized fromacetonitrile), 10 ml of toluene and 0.5 ml of water is initiallycharged. With stirring at 0° C., formaldehyde, obtained by priordepolymerization of 0.36 g (12 mmol) of paraformaldehyde at about 150°C., is passed in gaseous form together with a stream of nitrogen intothis mixture. After the addition has ended, stirring is continued at 20°C. for 30 minutes, and the mixture is then admixed with 0.82 g (10 mmol)of sodium thiocyanate and 1.2 g (10 mmol) of sodium hydrogen sulphate.The resulting reaction mixture is stirred at 20° C. for 2 hours andsubsequently diluted with 100 ml of dichloromethane. The solid isfiltered off and the liquid organic phase is concentrated under reducedpressure. This gives 3.28 g of a product which, according to HPLCanalysis, comprises 98.6% of2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiono-1-yl)-propane. Accordingly, the calculatedyield is 95% of theory.

Melting point: 157-158° C.

Example 5

At 0° C. and under an atmosphere of nitrogen, a mixture of 2.74 g (10mmol) of[2-(1-chloro-cycloprop-1-yl)-3-(2-chlorophenyl)-2-hydroxy]-propyl-1-hydrazine(which had been recrystallized from acetonitrile) and 10 ml of tolueneis admixed with stirring with 0.74 ml (10 mmol) of a 40% strengthformalin solution. After the addition has ended, the mixture is stirredat 20° C. for 30 minutes and then admixed with 0.82 g (10 mmol) ofsodium thiocyanate and 1.2 g (10 mmol) of sodium hydrogen sulphate. Thereaction mixture is stirred at 20° C. for 2 hours and subsequentlydiluted with 100 ml of dichloromethane. The solid is filtered off andthe liquid organic phase is concentrated under reduced pressure. Thisgives 3.3 g of a product which, according to HPLC analysis, comprises93.9% of2-(1-chloro-cycloprop-1-yl)-1-(2-chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiono-1-yl)-propane.Accordingly, the calculated yield is 90.2% of theory.

Melting point: 154-155° C.

Example 6

At 0° C. and under an atmosphere of nitrogen, a mixture of 2.74 g (10mmol) of[2-(1-chloro-cycloprop-1-yl)-3-(2-chlorophenyl)-2-hyxroxy]-propyl-1-hydrazine(which had been recrystallized from acetonitrile) and 10 ml of tolueneis successively admixed with stirring with 1.2 g (10 mmol) of sodiumhydrogen sulphate, 0.74 ml (10 mmol) of a 40% strength formalin solutionand 0.82 g (10 mmol) of sodium thiocyanate. After the addition hasended, the mixture is stirred at 20° C. for 2 hours and then dilutedwith 100 ml of dichloromethane. The solid is filtered off and the liquidorganic phase is concentrated under reduced pressure. This gives 3.4 gof a product which, according to HPLC analysis, comprises 83.1% of2-(1-chloro-cycloprop-1-yl)-1-(2-chlorophenyl)-2-hydroxy-3-(1,2,4-triazolidine-5-thiono-1-yl)-propane.Accordingly, the calculated yield is 83% of theory.

Melting point: 136-138° C.

Comparative Examples Example A

At −20° C., a mixture of 3.12 g (10 mmol) of2-(1-chloro-cycloprop-1-yl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-oland 45 ml of absolute tetrahydrofuran is admixed with 8.4 ml (21 mmol)of n-butyl-lithium in hexane and stirred at 0° C. for 30 minutes. Thereaction mixture is then cooled to −70° C., admixed with 0.32 g of (10mmol) of sulphur powder and stirred at −70° C. for 30 minutes. Themixture is warmed to −10° C., admixed with ice-water and adjusted to pH5 by addition of dilute sulphuric acid. The mixture is extractedrepeatedly with ethyl acetate, and the combined organic phases are driedover sodium sulphate and concentrated under reduced pressure. In thismanner, 3.2 g of a product which, according to gaschromatographicanalysis, comprises 95% of2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-3-(4,5-dihydro-1,2,4-triazole-5-thiono-1-yl)-propan-3-olare obtained. After recrystallization from toluene, the substance has amelting point of from 138° C. to 139° C.

Example B

With stirring, a mixture of 3.12 g (10 mmol) of2-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,0.96 g (30 mmol) of sulphur powder and 20 ml of absoluteN-methyl-pyrrolidone is heated at 200° C. for 44 hours. The reactionmixture is then concentrated under reduced pressure (0.2 mbar). Theresulting crude product (3.1 g) is recrystallized from toluene. In thismanner, 0.7 g (20% of theory) of²-(1-chloro-cycloprop-1-yl)-1-(2-chloro-phenyl)-3-(4,5-dihydro-1,2,4-triazole-5-thiono-1-yl)-propan-2-olis obtained in the form of a solid which melts at 138-139° C.

What is claimed is:
 1. A triazolidinethione of the formula

in which R¹ represents straight-chain or branched alkyl having 1 to 6carbon atoms, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting ofhalogen, alkoxy having 1 to 4 carbon atoms, alkoximino having 1 to 4carbon atoms in the alkoxy moiety and cycloalkyl having 3 to 7 carbonatoms, or  represents straight-chain or branched alkenyl having 2 to 6carbon atoms, where each of these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, alkoxy having 1 to 4 carbon atoms and cycloalkylhaving 3 to 7 carbon atoms, or  represents cycloalkyl having 3 to 7carbon atoms, where each of these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, cyano and alkyl having 1 to 4 carbon atoms, or represents aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1to 4 carbon atoms in the straight-chain or branched alkyl moiety, wherethe aryl moiety may in each case be mono- to trisubstituted by identicalor different substituents from the group consisting of halogen, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthiohaving 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or  representsaralkenyl having 6 to 10 carbon atoms in the aryl moiety and 2 to 4carbon atoms in the alkenyl moiety, where the aryl moiety may in eachcase be mono- to trisubstituted by identical or different substituentsfrom the group consisting of halogen, alkyl having 1 to 4 carbon atoms,alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms,halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1to 5 identical or different halogen atoms, halogenoalkylthio having 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms,cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonylhaving 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in thealkyl moiety, nitro and cyano, or  represents aroxyalkyl having 6 to 10carbon atoms in the aryl moiety and 1 to 4 carbon atoms in thestraight-chain or branched oxyalkyl moiety, where the aryl moiety may ineach case be mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, alkyl having 1 to 4carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 or 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or  represents arylhaving 6 to 10 carbon atoms, where each of these radicals may be mono-to trisubstituted by identical or different substituents from the groupconsisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 or 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand cyano, and R² represents straight-chain or branched alkyl having 1to 6 carbon atoms, where these radicals may be mono- to tetrasubstitutedby identical or different substituents from the group consisting ofhalogen, alkoxy having 1 to 4 carbon atoms, alkoximino having 1 to 4carbon atoms in the alkoxy moiety and cycloalkyl having 3 to 7 carbonatoms, or  represents straight-chain or branched alkenyl having 2 to 6carbon atoms, where each of these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, alkoxy having 1 to 4 carbon atoms and cycloalkylhaving 3 to 7 carbon atoms, or  represents cycloalkyl having 3 to 7carbon atoms, where each of these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of halogen, cyano and alkyl having 1 to 4 carbon atoms, or represents aralkyl having 6 to 10 carbon atoms in the aryl moiety and 1to 4 carbon atoms in the straight-chain or branched alkyl moiety, wherethe aryl moiety may in each case be mono- to trisubstituted by identicalor different substituents from the group consisting of halogen, alkylhaving 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthiohaving 1 to 4 carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and1 to 5 identical or different halogen atoms, halogenoalkoxy having 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or  representsaralkenyl having 6 to 10 carbon atoms in the aryl moiety and 2 to 4carbon atoms in the alkenyl moiety, where the aryl moiety may initiallybe mono- to trisubstituted by identical or different substituents fromthe group consisting of halogen, alkyl having 1 to 4 carbon atoms,alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms,halogenoalkyl having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkoxy having 1 or 2 carbon atoms and 1to 5 identical or different halogen atoms, halogenoalkylthio having 1 or2 carbon atoms and 1 to 5 identical or different halogen atoms,cycloalkyl having 3 to 7 carbon atoms, phenyl, phenoxy, alkoxycarbonylhaving 1 to 4 carbon atoms in the alkoxy moiety, alkoximinoalkyl having1 to 4 carbon atoms in the alkoxy moiety and 1 to 4 carbon atoms in thealkyl moiety, nitro and cyano, or  represents aroxyalkyl having 6 to 10carbon atoms in the aryl moiety and 1 to 4 carbon atoms in thestraight-chain or branched oxyalkyl moiety, where the aryl moiety may ineach case be mono- to trisubstituted by identical or differentsubstituents from the group consisting of halogen, alkyl having 1 to 4carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4carbon atoms, halogenoalkyl having 1 or 2 carbon atoms and 1 to 5identical or different halogen atoms, halogenoalkoxy having 1 or 2carbon atoms and 1 to 5 identical or different halogen atoms,halogenoalkylthio having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, cycloalkyl having 3 to 7 carbon atoms, phenyl,phenoxy, alkoxycarbonyl having 1 to 4 carbon atoms in the alkoxy moiety,alkoximinoalkyl having 1 to 4 carbon atoms in the alkoxy moiety and 1 to4 carbon atoms in the alkyl moiety, nitro and cyano, or  represents arylhaving 6 to 10 carbon atoms, where each of these radicals may be mono-to trisubstituted by identical or different substituents from the groupconsisting of halogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, halogenoalkylhaving 1 or 2 carbon atoms and 1 to 5 identical or different halogenatoms, halogenoalkoxy having 1 or 2 carbon atoms and 1 to 5 identical ordifferent halogen atoms, halogenoalkylthio having 1 or 2 carbon atomsand 1 to 5 identical or different halogen atoms, cycloalkyl having 3 to7 carbon atoms, phenyl, phenoxy, alkoxycarbonyl having 1 to 4 carbonatoms in the alkoxy moiety, alkoximinoalkyl having 1 to 4 carbon atomsin the alkoxy moiety and 1 to 4 carbon atoms in the alkyl moiety, nitroand cyano, wherein neither R¹ nor R² contain an heterocyclic ring. 2.The triazolidinethione of claim 1 wherein R¹ represents straight-chainor branched alkyl having 1 to 4 carbon atoms, where these radicals maybe mono- to tetrasubstituted by identical or different substituents fromthe group consisting of fluorine, chlorine, bromine, methoxy, ethoxy,propoxy, isopropoxy, alkoximino having 1 or 2 carbon atoms in the alkoxymoiety, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, or represents straight-chain or branched alkenyl having 2 to 5 carbonatoms, where each of these radicals may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, or  representscycloalkyl having 3 to 6 carbon atoms, where each of these radicals maybe mono- to trisubstituted by identical or different substituents fromthe group consisting of fluorine, chlorine, bromine, cyano, methyl,ethyl, propyl, isopropyl and tert-butyl, or  represents phenylalkylhaving 1 to 4 carbon atoms in the straight-chain or branched alkylmoiety, where the phenyl moiety may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or  represents phenylalkenyl having 2 to 4 carbon atomsin the alkenyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or  representsphenoxyalkyl having 1 to 4 carbon atoms in the straight-chain orbranched oxyalkyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or  representsphenyl which may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,and R² represents straight-chain or branched alkyl having 1 to 4 carbonatoms, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,alkoximino having 1 or 2 carbon atoms in the alkoxy moiety, cyclopropyl,cyclobutyl, cyclopentyl and cyclohexyl, or  represents straight-chain orbranched alkenyl having 2 to 5 carbon atoms, where each of theseradicals may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methoxy, ethoxy, propoxy, isopropoxy, cyclopropyl, cyclobutyl,cyclopentyl and cyclohexyl, or  represents cycloalkyl having 3 to 6carbon atoms, where each of these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, cyano, methyl, ethyl, propyl,isopropyl and tert-butyl, or  represents phenylalkyl having 1 to 4carbon atoms in the straight-chain or branched alkyl moiety, where thephenyl moiety may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,or  represents phenylalkenyl having 2 to 4 carbon atoms in the alkenylmoiety, where the phenyl moiety may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or  represents phenoxyalkyl having 1 to 4 carbon atomsin the straight-chain or branched oxyalkyl moiety, where the phenylmoiety may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,or  represents phenyl which may be mono- to trisubstituted by identicalor different substituents from the group consisting of fluorine,chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano.
 3. The triazolidinethione of claim 1 wherein R¹represents n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl ortert-butyl, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,methoximino, ethoximino, cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl, or  represents straight-chain or branched alkenyl having 2to 5 carbon atoms, where each of these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methoxy, ethoxy, propoxy,isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, or represents 1-methyl-cyclohexyl, cyclohexyl, 1-chloro-cyclopropyl,1-fluoro-cyclopropyl, 1-methyl-cyclopropyl, 1-cyano-cyclopropyl,cyclopropyl, 1-methyl-cyclopentyl or 1-ethyl-cyclopentyl, or  representsphenylalkyl having 1 or 2 carbon atoms in the straight-chain or branchedalkyl moiety, where the phenyl moiety may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluoromethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or  represents phenylalkenyl having 2 to 4 carbon atomsin the alkenyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluormethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or  representsphenoxyalkyl having 1 to 4 carbon atoms in the straight-chain orbranched oxyalkyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluormethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or  representsphenyl which may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano,and R² represents n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl ortert-butyl, where these radicals may be mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methoxy, ethoxy, propoxy, isopropoxy,methoximino, ethoximino, cyclopropyl, cyclobutyl, cyclopentyl andcyclohexyl, or  represents straight-chain or branched alkenyl having 2to 5 carbon atoms, where each of these radicals may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methoxy, ethoxy, propoxy,isopropoxy, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, or represents 1-methyl-cyclohexyl, cyclohexyl, 1-chloro-cyclopropyl,1-fluoro-cyclopropyl, 1-methyl-cyclopropyl, 1-cyano-cyclopropyl,cyclopropyl, 1-methyl-cyclopentyl or 1-ethyl-cyclopentyl, or  representsphenylalkyl having 1 or 2 carbon atoms in the straight-chain or branchedalkyl moiety, where the phenyl moiety may be mono- to trisubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, methyl, ethyl, tert-butyl, methoxy, ethoxy,methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio,chlorodifluormethoxy, difluoromethoxy, chlorodifluoromethylthio,methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl,nitro and cyano, or  represents phenylalkenyl having 2 to 4 carbon atomsin the alkenyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or  representsphenoxyalkyl having 1 to 4 carbon atoms in the straight-chain orbranched oxyalkyl moiety, where the phenyl moiety may be mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine methyl, ethyl, tert-butyl,methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy,trifluoromethylthio, chlorodifluoromethoxy, difluoromethoxy,chlorodifluoromethylthio, methoxycarbonyl, ethoxycarbonyl,methoximinomethyl, 1-methoximinoethyl, nitro and cyano, or  representsphenyl which may be mono- to trisubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,methyl, ethyl, tert-butyl, methoxy, ethoxy, methylthio, trifluoromethyl,trifluoromethoxy, trifluoromethylthio, chlorodifluoromethoxy,difluoromethoxy, chlorodifluoromethylthio, methoxycarbonyl,ethoxycarbonyl, methoximinomethyl, 1-methoximinoethyl, nitro and cyano.4. A triazolidinethione of the formula: